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(d, J = 5.5 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = 14.0, 19.4, 31.4, NMR (400 MHz, [D6]DMSO): δ = 4.93 (d, J = 6.0 Hz, 2H), 6.91 (d, J =
45.7, 67.8, 111.2, 114.8, 118.2, 121.6, 126.0, 127.2, 129.5, 129.8, 131.3, 5.5 Hz, 2H), 7.40–7.50 (m, 2H), 7.53 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H),
137.2, 141.5, 155.0, 158.7; MS (FAB): m/z 307 [M + H]+; HRMS (FAB):
m/z [M + H]+ calcd. for C20H22N2O 307.1810, found 307.1809.
7.57 (dd, J = 6.9, 1.8 Hz, 1H), 7.64 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H), 7.72
(d, J = 7.3 Hz, 1H), 7.78–7.92 (m, 5H), 8.12 (d, J = 5.5 Hz, 1H), 8.36
(d, J = 7.8 Hz, 1H); 13C-NMR (100 MHz, [D6]DMSO) δ = 44.6, 110.3,
118.4, 123.6, 125.5, 125.9, 126.2, 126.5, 126.6, 127.1, 128.0, 128.2,
130.3, 132.6, 133.5, 137.2, 139.1, 142.0, 155.7; MS (FAB): m/z 285
[M]+; HRMS (FAB): m/z [M]+ calcd. for C17H16N2 284.1313, found
284.1313; Anal. Calcd for C20H16N2·0.1H2O: C, 83.95; H, 5.64; N, 9.79;
found C, 83.94; H, 5.57; N, 9.74.
N-[4-(Pentyloxy)benzyl]isoquinolin-1-amine (3k): Following the
general procedure III, 3k was obtained as a yellow oil. Yield 214 mg
(67 %); IR (KBr) /cm–1: ν = 3444, 1624; 1H-NMR (400 MHz, CDCl3) δ =
˜
0.91 (t, J = 7.3 Hz, 3H), 1.25–1.50 (m, 4H), 1.74 (quin, J = 6.9 Hz, 2H),
3.87 (t, J = 6.9 Hz, 2H), 4.68 (d, J = 5.0 Hz, 2H), 5.48 (brt, J = 4.6 Hz,
1H), 6.80 (d, J = 8.2 Hz, 2H), 6.90 (d, J = 6.0 Hz, 1H), 7.27 (d, J =
8.7 Hz, 2H), 7.31 (ddd, J = 8.2, 6.9, 0.9 Hz, 1H), 7.49 (ddd, J = 8.2,
6.9, 0.9 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 8.00
N-Benzylquinolin-2-amine (3q):[35] Following the general proce-
dure II, 3q was obtained as a white solid. Yield 192 mg (82 %); m.p.
(d, J = 6.0 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = 14.2, 22.6, 28.4, 100–102 °C; IR (KBr) /cm–1: ν = 3265, 1622; 1H-NMR (400 MHz,
˜
29.1, 45.7, 68.1, 111.2, 114.8, 118.2, 121.6, 126.0, 127.2, 129.5, 129.8,
CDCl3): δ = 4.73 (d, J = 5.7 Hz, 2H), 5.03 (brs, 1H), 6.62 (d, J = 8.9 Hz,
131.3, 137.2, 141.5, 155.1, 158.7; MS (FAB): m/z 321 [M + H]+; HRMS 1H), 7.22 (ddd, J = 8.0, 6.9, 1.1 Hz, 1H), 7.27–7.42 (m, 5H), 7.54 (ddd,
(FAB): m/z [M + H]+ calcd. for C21H25N2O 321.1967, found 321.1966.
J = 8.5, 7.1, 1.6 Hz, 1H), 7.59 (dd, J = 1.4, 8.0 Hz, 1H), 7.71 (dd, J =
8.4, 0.7 Hz, 1H), 7.81 (d, J = 8.9 Hz, 1H); 13C-NMR (100 MHz, CDCl3)
δ = 45.9, 111.4, 122.2, 123.6, 126.3, 127.4, 127.5, 127.8, 128.7, 130.0,
137.5, 139.4, 148.0, 156.7; MS (FAB): m/z 235 [M + H]+.
N-(4-Methylbenzyl)isoquinolin-1-amine (3l): Following the gen-
eral procedure II, 3l was obtained as a brown oil. Yield 186 mg
(75 %); IR (KBr) /cm–1: ν = 3310, 1623; 1H-NMR (400 MHz, CDCl3):
˜
δ = 2.36 (s, 3H), 4.76 (d, J = 5.0 Hz, 2H), 5.39 (brs, 1H), 6.96 (dd, J =
6.0, 0.5 Hz, 1H), 7.18 (d, J = 7.8 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.43
(ddd, J = 8.5, 7.1, 1.4 Hz, 1H), 7.58 (ddd, J = 8.0, 6.9, 1.1 Hz, 1H),
7.69 (d, J = 8.0 Hz, 1H), 7.72 (d, J = 8.2 Hz, 1H), 8.04 (d, J = 6.0 Hz,
1H); 13C-NMR (100 MHz, CDCl3) δ = 21.1, 45.9, 111.2, 118.0, 121.4,
125.9, 127.2, 128.1, 129.4, 129.7, 136.3, 137.1, 141.4, 154.9; MS (FAB):
m/z 249 [M + H]+. HRMS (FAB): m/z [M + H]+ calcd. for C17H16N2
249.1392, found 249.1392.
N-Benzylquinolin-3-amine (3r):[36] Following the general proce-
dure II, 3r was obtained as a yellow solid. Yield 187 mg (79 %); m.p.
96–100 °C; IR (KBr) /cm–1: ν = 3344, 1615; 1H-NMR (400 MHz, CDCl3):
˜
δ = 4.43 (m, 3H), 7.02 (d, J = 2.8 Hz, 1H), 7.29–7.47 (m, 7H), 7.58
(dd, J = 6.0, 3.7 Hz, 1H), 7.94 (dd, J = 6.2, 3.4 Hz, 1H), 8.49 (d, J =
2.8 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = 48.0, 110.5, 125.0, 126.0,
127.0, 127.5, 127.6, 128.9, 129.1, 129.4, 138.2, 141.4, 142.2, 143.3;
MS (FAB): m/z 235 [M + H]+.
N-(4-Methylbenzyl)isoquinolin-8-amine (3m): Following the gen- N-Benzylquinolin-6-amine (3s):[37] Following the general proce-
eral procedure I, 3m was obtained as a white solid. Yield 236 mg
dure II, 3s was obtained as a yellow solid. Yield 214 mg (91 %); m.p.
(95 %); m.p. 120–121 °C; IR (KBr) /cm–1: ν = 3269, 1568; 1H-NMR
124–125 °C; IR (KBr) /cm–1: ν = 3316, 1622; 1H-NMR (400 MHz,
˜
˜
(400 MHz, [D6]DMSO): δ = 2.26 (s, 3H), 4.47 (d, J = 5.5 Hz, 2H), 6.45
(d, J = 7.3 Hz, 1H), 7.02 (d, J = 7.8 Hz, 1H), 7.12 (d, J = 7.8 Hz, 2H),
7.30 (d, J = 8.2 Hz, 2H), 7.38 (t, J = 8.2 Hz, 1H), 7.54 (t, J = 6.0 Hz,
1H), 7.60 (d, J = 5.5 Hz, 1H), 8.39 (d, J = 5.5 Hz, 1H), 9.63 (s, 1H);
13C-NMR (100 MHz, [D6]DMSO) δ = 21.2, 46.4, 105.6, 113.6, 118.8,
120.8, 127.4, 129.5, 132.2, 136.2, 136.9, 137.0, 143.3, 145.3, 147.4;
MS (FAB): m/z 249 [M + H]+. HRMS (FAB): m/z [M + H]+ calcd. for
CDCl3): δ = 4.44 (m, 3H), 6.72 (d, J = 2.8 Hz, 1H), 7.13 (dd, J = 9.2,
2.5 Hz, 1H), 7.25 (dd, J = 8.4, 4.4 Hz, 1H), 7.28–7.52 (m, 5H), 7.89 (d,
J = 8.7 Hz, 2H), 8.61 (dd, J = 4.1, 1.6 Hz, 1H); 13C-NMR (100 MHz,
CDCl3) δ = 48.3, 103.3, 121.3, 121.4, 127.4, 127.5, 128.7, 130.1, 130.3,
133.9, 138.6, 143.3, 145.9, 146.3; MS (FAB): m/z 235 [M + H]+.
N-(4-Methoxybenzyl)quinolin-2-amine (3t):[38] Following the
general procedure II, 3t was obtained. Yield 176 mg (66 %) as a
C17H16N2 249.1392, found 249.1392.
yellow oil; IR (KBr) /cm–1: ν = 3285, 1608; 1H-NMR (400 MHz, CDCl3):
˜
N-(2-Methylbenzyl)isoquinolin-1-amine (3n):[34] Following the δ = 3.80 (s, 3H), 4.65 (d, J = 3.9 Hz, 2H), 5.05 (brs, 1H), 6.62 (d, J =
general procedure II, 3n was obtaine as a yellow solid. Yield 174 mg
8.7 Hz, 1H), 6.88 (d, J = 8.7 Hz, 2H), 7.22 (ddd, J = 8.0, 7.1, 1.4 Hz,
(70 %); m.p. 77–80 °C; IR (KBr) /cm–1: ν = 3251, 1623; 1H-NMR 1H), 7.34 (d, J = 8.7 Hz, 2H), 7.54 (ddd, J = 8.5, 6.9, 1.6 Hz, 1H ), 7.59
˜
(400 MHz, CDCl3): δ = 2.41 (s, 3H), 4.78 (d, J = 4.8 Hz, 2H), 5.24 (brs,
1H), 6.98 (d, J = 6.0 Hz, 1H), 7.16–7.25 (m, 3H), 7.38 (d, J = 7.1 Hz,
1H), 7.43 (ddd, J = 8.2, 6.8, 1.1 Hz, 1H), 7.58 (ddd, J = 8.0, 6.9, 1.1 Hz,
(dd, J = 7.7, 1.4 Hz, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.81 (d, J = 8.5 Hz,
1H ); 13C-NMR (100 MHz, CDCl3) δ = 45.5, 55.4, 111.4, 114.1, 122.2,
123.6, 126.2, 127.5, 129.2, 129.7, 131.4, 137.5, 156.8, 159.0; MS (FAB):
1H), 7.69 (d, J = 4.4 Hz, 1H), 7.71 (d, J = 5.0 Hz, 1H), 8.05 (d, J = m/z 265 [M + H]+.
6.0 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = 19.1, 44.3, 111.1, 118.0,
N-(3-Methylbenzyl)quinolin-2-amine (3u): Following the general
121.4, 125.9, 126.2, 127.2, 127.7, 129.0, 129.7, 130.6, 137.0, 141.4,
procedure II, 3u was obtained as a colorless oil. Yield 152 mg (62 %);
154.8; MS (FAB): m/z 249 [M + H]+.
1
IR (KBr) /cm–1: ν = 3277, 1619; H-NMR (400 MHz, CDCl3): δ = 2.34
˜
N-(4-Isopropylbenzyl)isoquinolin-1-amine (3o): Following the (s, 3H), 4.67 (d, J = 5.0 Hz, 2H), 5.07 (brs, 1H), 6.61 (d, J = 9.2, 1.4 Hz,
general procedure III, 3o was obtaine as a yellow oil. Yield 206 mg
1H), 7.09 (d, J = 7.3 Hz, 1H), 7.15–7.30 (m, 4H), 7.53 (dd, J = 8.2,
6.9 Hz, 2H), 7.58 (d, J = 7.8 Hz, 1H), 7.71 (d, J = 8.7 Hz, 1H), 7.80 (d,
J = 8.7 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = 21.5, 46.0, 111.4,
122.2, 123.6, 124.9, 126.3, 127.5, 128.2, 128.6, 128.7, 129.7, 137.5,
138.4, 139.3, 148.1, 156.9; MS (FAB): m/z 249 [M + H]+; HRMS (FAB):
(75 %); IR (KBr) /cm–1: ν = 3447, 1623; 1H-NMR (400 MHz, CDCl3):
˜
δ = 1.23 (d, J = 7.3 Hz, 6H), 2.88 (sep, J = 6.9 Hz, 1H), 4.74 (d, J =
5.0 Hz, 1H), 5.46 (brs, 1H), 6.91 (d, J = 5.5 Hz, 1H), 7.18 (d, J = 7.8 Hz,
2H), 7.28–7.36 (m, 3H), 7.50 (dd, J = 7.8, 6.9 Hz, 1H), 7.62 (d, J =
8.2 Hz, 2H), 8.01 (d, J = 6.0 Hz, 1H); 13C-NMR (100 MHz, CDCl3) δ = m/z [M + H]+ calcd. for C17H16N2 249.1392, found 249.1391.
24.2, 34.0, 46.0, 111.3, 118.2, 121.6, 126.0, 126.9, 127.3, 128.4, 129.8,
N-Benzyl-1-isobutyl-1H-imidazo[4,5-c]quinolin-4-amine (3v):[39]
A mixture of Imiquimod (240 mg, 1 mmol), palladium(II) acetate
(24 mg, 0.1 mmol), sodium diphenylphosphinobenzene-3-sulfonate
136.9, 137.2, 141.6, 148.2, 155.1; MS (FAB): m/z 277 [M + H]+; HRMS
(FAB): m/z [M + H]+ calcd. for C19H20N2 277.1705, found 277.1705.
N-(Naphthalen-2-ylmethyl)isoquinolin-1-amine (3p): Following
(TPPMS, 72 mg, 0.2 mmol) and benzyl alcohol (2) (515 μL, 5 mmol)
in H2O (4 mL) was heated at 140 °C for 18 h in a sealed tube under
air. After cooling, the reaction mixture was poured into water and
the general procedure III, 3p was obtained as a white solid. Yield
1
202 mg (71 %); m.p. 134–136 °C; IR (KBr) /cm–1: ν = 3417, 1619; H-
˜
Eur. J. Org. Chem. 0000, 0–0
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim